Method of producing chemical compounds by ion transfer



y 0, 1958 P. KOLLSMAN 2,835,632-

METHOD OF PRODUCING CHEMICAL COMPOUNDS BY ION TRANSFER Filed May 2, 1955 B mmvroa. f Paul Ko/lsman y lh-i-ML'$.M

A 7'TORMEY United States Patent Q METHOD OF PRODUCHNG CHEMICAL COM- POUNDS BY ION TRANSFER Paul Kollsman, New York, N. Y.

Application May 2, 1955, Serial No. 505,355

3 Claims. (Cl. 204-180) chemical compounds in solution, for example salt in water, split into charged atomic or molecular particles. These charged particles can be caused to move in a controlled fashion under the influence of an impressed electrical potential, which may conveniently be created between a positively charged anode and a negatively charged cathode. The negatively charged particles tend to travel towards the anode and are called anions for this reason, and the positively charged particles are attracted by the cathode and are called cations.

Means are also known for selectively influencing, restricting, or impeding the movement of ions which are under the influence of an impressed electric bias. Substances are known which, when formed into a thin wall or membrane, are effective fluid-barriers adapted to separate fluid volumes from one another, but which permit anions to pass therethrough while obstructing the passage of cations, and other substances are known which may be shaped into membranes effective as fluid barriers but capable of permitting cations to pass therethrough while restricting the passage of anions.

Still other substances are known which, in the form of a membrane, permit both anions and cations to pass from one volume of fluid into another and from the other volume of fluid into the one volume of fluid. The last named substances are also useful as ion-passage-discrimi-- nating fluid barriers in an arrangement in which the impressed electrical bias causes ions of one sign to pass through the membrane while ions of the opposite sign tend to move in the opposite direction, away from the membrane.

The aforementioned principle makes it possible, for example, to reduce the salt content saline solutions by. causing ions of the salt to pass from one fluid chamber through appropriate ion-passage-discriminating membranes into other chambers, thus depleting the one volume of fluid of its salt content.

Similarly, it is possible to increase the salt concentration of a volume of saline fluid by transferring into the volume ions removed from other volumes of fluid.

In either instance, the desired product, that is the fluid of reduced or of increased salt content, is the same I in character as the fluid originally treated, except for the degree of concentration.

The present invention is concerned with the production of new compounds which, as far as their chemical composition is concerned are dissimilar from the compounds from which they were produced.

whereas solution D comprises cations B1 and anions A2.

It is thus possible to produce relatively expensive product compounds by ion transfer from relatively inexpensive source compounds with relatively simple equip ment at a relatively low expense of electric energy.

While, in the majority of cases, it will be the object to produce one or two compounds from less expensive source compounds, the basic concept underlying the present invention may be carried further to produce, in the same apparatus, by the same method, and at the same time, a greater number of product compounds from a correspondingly greater number of source compounds.

The present method may be carried out with relatively simple and inexpensive equipment olfering the particular advantage that no electrodes are present in.the individual compartments or cells in which ion depletion and ion enrichment takes place, except in the two terminal compartments or cells of the apparatus. It is thus possible to carry out reactions which would be disturbed by the presence of electrodes, or which would be adversely alfected by, or which would adverselyafi'ect, the material from which the electrodes-are composed. Thus it is not necessarily an object to produce a costlier product from less expensive source compounds, but it is fre-' quently desirable to reduce the cost of operation, for xample by eliminating the consumption and the necessity of replacement of electrodes. increased degree of the economy is brought about, even in instances where the product does not command a much higher market price than the source compounds from which it was produced.

In still other instances the present invention permits certain compounds to be produced from certain readily available materials which do not lend themselves to economic-processing according to conventional methods. It is thus easily seen that the invention has a very' Generally, it may be stated i broad field of application. that the invention relates to processes involving the production of certain chemical compositions from other compositions in which certain constituents of the product occur singly, but not combined. Such processes are sometimes referred to as metathesis.

The various objects, features and advantages of this invention will appear more fully from the detailed description which follows, accompanied by drawings showing, for the purpose of illustration, an apparatus for practising the invention.

The invention also resides in certain new and original steps and combination of steps, as hereinafter set forth and claimed.

Although the characteristic features of this invention which are believed to be novel will be particularly pointed out in the claims appended hereto, the invention itself, its objects and advantages, and the manner in which it may be carried out will be better understood by referring to the following description taken in connection with the accompanying drawings forming a part of it, in.

which:

Figure 1 is a diagrammatic representation, in vertical Patented May 20, 1953 More generally, it is In this manner an Figure 2 is an elevational view taken on line 2-2 of Figure 1.

In the following description and in the claims, various details will be identified. by specific means for convenience. Thenames, however, are. intended to be-as. generic in their application as the art will permit- Like reference characters. refer to like parts in theseveral figures ofthe drawings.

Inrthe drawings accompanying. and forming a part of this specificatiomcertain specific. disclosure of the invention is made for. the purpose of explanation of broader aspects. of the'invention, but it is understood that the details. may be'modified in various respects without departure. from. the principles of the. invention and that the invention may be applied-to,.and practiced by, other structures than the one shown.

The principle and features. of. theinvention are readily understood by first considering the basic structure of an apparatusfor practising it. Figure l is a-diagrammatic illustration of an apparatus particularlydesigned for producing one or two product compounds'from' source compounds having a different chemical composition than the source compounds by atransfer of ions from certain volumes of solution into other volumes.

A. tank 11 is subdivided into aplurality of chambers or cells by fiuid-separating ion-passage-discriminating walls or membranes made from asuitable composition or material impartingto. the walls of membranes. the desired ion-passage-discriminating properties under the influence of a'certain. electric bias as will presently appear. Thus certain membranes arepermeable to ions of one sign and passage resistant toionsof the opposite sign, while certain other membranes are. ofa type permeable to ions of the opposite sign. It is. frequently advantageous, but in no way indispensable,. that the membranes of the latter type which are permeable to ions of the opposite sign arealso passage resistant to ions of the one sign. However, if the latter membranes are permeable to ions of both signs, controlled ion. transfer is still accomplished because of theinfluence of theelectric bias and. of the tendency of the solution to. maintain an ionic. balance. This willbecome apparent from a consideration of the operation of the apparatus illustrated in. the drawings. Nevertheless, it. may simplify the. understanding of the apparatusifit is assumed. that one type of membranes is. employed which is permeable to ions of one sign and passage. resistant to. ions. of the opposite signwhile the other type of membranes ispermeableto ions of the opposite sign and passage resistant toions' of the one: sign.

Specifically it may be assumed that membranes 12 are anion-permeable and cation-passage-resistant,. while other. membranes are cation-permeable and anion-passageresistant or at leasttcati'on-permeable although not necessarily also anion-passage-resistant. The membranes are arranged in alternatingsequence with respect to traverse of the tank fromone end tothe other-so that a-membrane of one type is followedby a membrane of the other type which, in turn, is followed. by a membrane of the one type and so forth. 1

The chambers orcells may be classified into terminal chambers 14 and 15' containing electrodes 16 and 17 and intermediate chambers 18, 19, and 21.

The electrode 16 is connected to the negative pole of a source of=electric energy (not shown), thus becoming a cathode and the electrode 17 is connected to the positive pole of the source, making theelectrode 17 an anode.

The intermediate cells may conveniently be grouped into decomposition chambers 18 and 19 and composition chambers 20 and 21, depending on the character of the electrodialytic action taking place therein. The decomposition chambers 18 and 19 may be made narrower than the composition chambers 20 and 21, width being measured between the bordering membranes, but the dimensions may be varied otherwise to suit the particular requirements of each installation. in the diagrammatic A.- drawings chambers of equal width are shown to simplify the illustration.

Speaking first of the decomposition chambers 18 and 19, means are provided for supplying fluid to these chambers. These fluid supply means may be of any suitable form and are shown in the illustrated example as comprising a first source-fluid supply duct 22 and a second source-fluid supply duct 23. The duct 22 is manifolded to supply the decomposition chambers 18 and through branches 24, and the second source-fluid supply duct 23 is manifolded to supply the decomposition chambers 19 through branches 25.

As will later be seen, the source-fluids are depleted of ions during passage through the decomposition chambers 18 and 19 and the remaining ion-depleted fluid is withdrawn from the chambers through withdrawal ducts 26 and 27. Duct 26 is manifolded to chambers 18 by branches 28 and the withdrawal duct 27 is manifolded to the decomposition chambers. 19 by branches 29.

Productfluidis withdrawn from the composition chambers 20 through a first product-fluid withdrawal duct 30 having branches 31, and a second product-fluid withdrawal duct 32; is manifolded to the composition chambers 21 by branches 33.

Fluid into which ions are being transferred in the composition chambersv may be caused to accumulate in the composition chambers by reason of fluid transfer from the decomposition chambers, making it unnecessary to supply additional fluid to the composition chambers. In. many instances the transfer of ions through the membranes is accompanied by a transfer of a' fluid sufficient for operation of the apparatus. However, in instances. where the volume of fluid thus transferredis not suflicient, fluid may be supplied through further ducts 34 and 35. The supply duct 34 is manifoldedv to the composition chambers 20-by branches 36,. and the supply duct 35 is manifolded to the composition chambers 21 by branches 37.

The fluid supplied through these ducts is selected with regard to the chemical composition of the product to be composed. The fluid may simply be a solvent or diluent for the product or it may contain additional components which are to enter. into the composition. The fluid may alsobe of a character causing the product formed in the composition chambers by ion transfer to precipitate. All these possibilities. will. be evident from a consideration of the. method about to be described and of the operation" of. the apparatus hereinafter disclosed in greater detail.

Separate ducts: 38, 39, 40 and 41 supply fluid to,.and withdraw from, the. terminal chambers 14' and 15 containing' the electrodes 16 and 17. The fluid of the terminal chambers is preferably handled separately because of certainelectro-chemical reactions which may be induced by the physicalpresence of the electrodes in these chambers making, it generally undesirable to mix: the product of the terminal chambers with the fluids: withdrawn from the composition chambers or from the decomposition chambers.

From the arrangement ofthe ducts it is evident that the direction of flow through the composition chambers is opposed to the flow through the decomposition chambers. By proper dimensioning of the ducts, or by other convenient means, such asflow restrictions in the ducts, the volumes of fluid passing through the several chambers may be adjustedto predetermined ratios, depending on the. degree of concentration'to be produced in the composition chambers and other factors governing the operation of the apparatus.

The operation of the illustrated apparatus may be conveniently explained by a specific example. It may be assumed that an aqueous solution of hydrogen bromide is supplied through the ducts. 22 and that an aqueous .solutionof potassium chloride is supplied through the supply duct 23. It'mayfurther 'be assumed" that the trical potential and that product chambers 20 and 21 are filled with a fluid, for example water, having a conductivity sufficient to cause a flow of current to be established between the electrodes. The hydrogen bromide in I the decomposition chambers splits into hydrogen cations and bromide anions. The hydrogen cations move towards the cathode and pass through the cation-permeable membranes 13, thus accumulating in the chambers 20. The bromine anions move in the opposite direction and pass through the anion permeable membranes 12 and accumulate in the chambers 21.

Similarly, the potassium chloride splits into potassium cations and chloride anions. The potassium cations move towards the cathode and pass through the cation permeable membranes 13, thus accumulating in the chambers 21. The chlorine anions travel in the opposite direction and pass through the anion permeable membranes 12. p

The exit of the hydrogen cations from the composition chambers 20 is barred by the membranes 12 which are cation-passage-resistant. In the same manner the exit of the potassium cations from the chambers 21 is barred by the cation-passage-resistant membranes 12.

Considering now the anions, the bromine anions cannot leave the chambers 21 into which they were transferred since the membranes 13 are anion-passage-resistant. For the same reasons chlorine anions are prevented by the membranes 13 from leaving the chambers 20 into which they were transferred.

The accumulation of potassium and bromine ions in the chambers 21 leads to the formation of potassium bromide and the accumulation of hydrogen and chlorine ions in the chambers 20 leads to the formation of hydrogen chloride in the chambers 20.

Thus the constituents of the source products, hydrogen, bromine, potassium and chlorine entering the process are caused to combine as new and different compounds potassium bromide and hydrochloric acidwhich are then withdrawn from the apparatus as products of the process. No electrodes are physically present in the chambers in which the decomposition and the composition takes place and the process may be carried out continuously. In a similar manner sodium sulphate and water may enter the apparatus or process as source compounds to produce sulphuric acid and sodium hydroxide under the influence of an electric current.

The foregoing examples are therefore merely illustrative of the basic principle of decomposing a first compound A in solution containing cations A1 and anions A2, decomposing a further source compound B in solution comprising cations B1 and anions B2, and so forth,

to produce new compounds in which a first compound comprises cations A1 and anions B2, and a second compound comprises cations B1 and anions A2, and so forth.

The products may be withdrawn from the apparatus in solution, or they may be caused to precipitate by adding further substances to the fluids supplied through ducts 34 and 35 causing such precipitation. It is also obvious that additional components'for the product compounds may be introduced as part of the fluid flow entering the process through ducts 34 and 35.

The fluid depleted of hydrogen and bromine ions is withdrawn through the duct 26 and the fluid depleted of potassium and chlorine is withdrawn through the duct 27.

A supply of fluid through the ducts 34 and 35 may be dispensed with, if a sufficient volume of fluid passes through the membranes 12 and 13 incidental to the transfer of ions.

A particular feature of the counterflow arrangement of the illustrated apparatus is its favorable effect on the current density and the current distribution. It is evidently desirabel to have the greatest current density near the bottom of the chambers in order to transfer the greatest possible number of ions per unit of time from the flow entering the decomposition chambers. A high current density near the bottom of the chambers is promoted by composition chambers so arranged that the greatest con-.

centration and, hence, the greatest conductivity is likewise near the bottom and not near the top, as it would be in an arrangement which does not employ the principle of opposite flow on opposite sides of the membranes.

Fluid may enter and leave the terminal compartments in any desired direction. The ducts 38 and 40 may be inflow ducts, and the ducts 39 and 41 may be discharge ducts, or the ducts 38 and 40 may be discharge ducts and the ducts 39 and 41 be supply ducts or the flow through one terminal compartment may be opposed to the flow through the other terminal compartment.

It was previously mentioned that it is not necessary that all the membranes which are permeable to ions of the one sign are also passage resistant to ions of the opposite sign. It is quite satisfactory that certain membranes are permeable to ions of both signs. Assuming for example that the membranes bordering the chambers 18 are permeable to ions of both signs, this will not interfere with the transfer of hydrogen cations into the chamber 20 nor with the transfer of bromine anions into the chamber 21, since the electric bias causes the ions to move in prescribed directions. As a result the hydrogen cations will accumulate along the membrane 12 bordering the chamber 20, this membrane being cation-passage-resistant and the formation of hydrochloric acid will take place as soon as chlorine ions enter the chamber 20 through the membrane 12.

A similar situation prevails in the chamber 21 where bromine ions tend to accumulate along the anion-passageresistant membrane 13 bordering the chamber 21. P0- tassium ions passing through the membrane 13 therefore tend to combine electrically with the bromine ions rather closely to the membrane 13 and there is no inducement for the potassium ions to travel further, even though the next membrane which they will encounter is not anionpassage-resistant This substitution of membranes permeable to ions of both signs for certain membranes permeable to passage of ions of one sign but resistant to passage of ions of the opposite sign is sometimes advantageous from a standpoint of economy, either by reasonof the fact that substi tuted membranes are less expensive, or more durable, or

have a higher conductivity thereby reducing the power requirement.

In the illustrated form of apparatus composition chain- 'bers and decomposition chambers alternate, but it is evident that diiferent reactions take place in successive decomposition chambers and in successive composition chambers. In 'an apparatus to which two source compounds are supplied and from which two product compounds are withdrawn the same reaction occurs in every second decomposition chamber and in every second composition chamber. Since decomposition chambers alternate with composition chambers, the manifolding of all ducts is in units of four. It logically follows that three source compounds and three product compounds require manifolding in units of six, and so forth.

For the purpose of specific tests a nine compartment apparatus, containing compartments Nos. 1 to 9, was constructed, comprising, in this order: a cathode--a cation membrane-an anion membra'ne-a cation membrane-an anion membranea cation membrane-an anion membrane-a cation membranean anion membrane-an anode; electrodes consisting of platinum, membranes spaced 1 millimeter from one another, the membranes measuring 25 x x 1 mm. (exposed surface) and produced according to the disclosure of Wyllie and Patnode, Journal of Phys. and Colloid Chemistry, vol. 54, pages 204 to 226, published February 1950, the specific data being as follows:

The cation membranes were composed of granules of 7 100 mesh size of Amberlite IR-120 in Na form constituting 70 percent of the total membrane material and polystyrene granules of 200 mesh size constituting 30 percent of the total membrane material.

The anion membranes were composed of granules of 100 mesh size of Amberlite IRA-400 in C1 form constituting 70 percent of the total membrane material and polystyrene granules of 200 mesh size constituting 30 percent of the total membrane material.

The aforementioned ion exchange materials were known and commercially available in or before 1949. (See F. C. Nachod, Ion Exchange, pages 385 to 388, Academic Press, New York, 1949.)

The molding of membranes took place under pressure of 3000 lb./sq. in. at 140 C. maintained for one minute in a mold cavity and produced membranes of 1 mm. thickness.

Example 1.--Prduction 0f KBr and HCl from HBr and KCl The deionization compartments Nos. 2 and 6 were supplied with an aqueous KCl solution containing 745 mg. KCl per 1000 cc. of water, flow direction upward;

The deionization compartments No. 4 and 8 were supplied with an aqueous HBr solution containing 809 mg. HBr per 1000 cc. of water, flow direction upward;

The ionization compartments Nos. 3, 5 and 7 were supplied with water, flow direction downward;

The electrode compartment No. 1 was also supplied with the aqueous HBr solution containing 809 mg. HBr per 1000 cc. of water, flow direction downward;

The electrode compartment No. 9 was supplied with the aqueous KCl solution containing 745 mg. KCl per 1000 cc. of water, flow direction downward;

A D. C. potential of the order of 5 v. was applied and adjusted to cause an electric current of 50 ma. to flow through the apparatus. Observation time: one hour after an initial warm-up period of about ten minutes.

ResuIts.-Product outflow from compartments Nos. 3 and 7 totaling 184 cc./h. containing 64 mg. HCl;

Product outflow from compartment No. 5 totaling 99 cc./h. containing 107 mg. KBr;

Product outflow from compartments Nos. 2 and 6 totaling 511 cc./h. of KCl solution (not quantitatively analyzed);

Product outflow from compartments Nos. 4 and 8 totaling 496' cc. of HBr solution (not quantitatively analyzed);

Eletcrode compartment N0. 1-outflow 561 cc./h. of an aqueous solution containing HBr and KBr;

Electrode compartment No. 9-outflow totaling 543 cc./'h. of an aqueous solution containing KCl and Br.

Example 2.--Pr0ducti0n of LiF and NaCl from LiCl and NaF The deionization compartments Nos. 2 and 6 were supplied with an aqueous NaF solution containing 4.2 g. NaF per 1000 cc. of water, flow direction upward;

The deionization compartments Nos. 4 and 8 were supplied with an aqueous LiCl solution containing 4.24 LiCl per 1000 cc. of water, flow direction upward;

The ionization compartments Nos. 3, 5 and 7 were supplied with water, flow direction downward;

The electrode compartment No. 1 was also supplied with the aqueous NaF solution containing 4.2 g. NaF per 1000 cc. of water, flow direction downward;

The electrode compartment No. 9 was supplied with the aqueous LiCl solution containing 4.24 LiCl per 1000 cc. of water, flow direction downward;

A D. C. potential of the order of 5 v. was applied and adjusted to cause an electric current of 100 ma. to flow through the apparatus. Observation time: one hour after an ititial warm-up period of about fifteen minutes. Results.Product outflows from compartments Nos. 3 and 7 totaling 163.3 cc./h. containing 95 mg. LiF;

Product outflow from compartment No. 5 totaling 91.6 cc./h. containing 103 mg. NaCl;

Product outflow from compartments Nos. 2 and 6 totaling 411 cc./h. of NaF solution (not quantitatively analyzed);

Product outflow from compartments Nos. 4 and 8 totaling 424.5 cc. of LiCl solution (not quantitively analyzed);

Electrode compartment No. 1outfiow 406 cc./h. of an aqueous solution containing NaF and NaOH;

Electrode compartment No. 9outfiow totaling 417 cc./h. of an aqueous solution containing LiCl and C1 Evidently the invention may be applied to, and practised by, various forms of apparatus and is not limited to the specific device illustrated in the drawings. Likewise many kinds of chemical compositions may be decomposed, recomposed or transformed by treatment according to the invention.

In this connection ions of composition may even'be replaced by larger electrically charged particles of colloidal size by treatment according to the present method and in the described type of apparatus.

Thus numerous changes, additions, omissions, substitutions and modifications in the apparatus and method steps, as well as other applications of the method and apparatus may be made without departing from the spirit, the teaching, and the principles of the invention.

What is claimed is:

1. The process of forming two chemically dissimilar ionic product compounds in solvated electrically conduc tive form by selective transfer into other fluid volumes of ionic constituents of two chemically dissimilar source compounds in ionic solution form, the method comprising, disposing between an anode chamber and a cathode chamber a plurality of volumes of electrodialytic liquid in this order: a first source compound in ionic solution form, a liquid capable of maintaining a first product compound to be formed in solvated and electrically conductive form, a second source compound in ionic solution form, a liquid capable of maintaining a second product compound to be formed in solvated and electrically conductive form, and a further volume of said first source compound in ionic solution form, said first source compound being so selected as to comprise an ionic constituent of one polarity of said first product compound to be formed and an ionic constituent of the opposite polarity of said second product compound to be formed, said second source compound being so selected as to comprise an ionic constituent of said opposite polarity of said first product compound to be formed and an ionic constituent of said one polarity of said second product compound to be formed; establishing controlled ionic communication between said volumes by permselective barriers arranged in alternating order, each second barrier being permeable to ions of one polarity and passage resistant to ions of the opposite polarity, the remaining barriers being permeable to ions of said opposite polarity; applying an electrical direct potential to said anode and said cathode to drive the ionic constituents of said two source compounds through said barriers into said solution volumes to form two distinct product compounds, the first product compound comprising a constituent of one polarity of one source compound and a constituent of the opposite polarity of the other source compound, the other product compound comprising a constituent of said opposite polarity of said one source compound and a constituent of said one polarity of said other source compound.

2. The process of forming by the action of an electric current two chemically dissimilar product compounds in ionic solution form from the components of two chemically dissimilar source compounds in ionic solution form, the process comprising, disposing between an anode chamber and a cathode chamber alternately arranged source fluid chambers and product fluid chambers separated by alternately arranged permselective anion mem branes and cation membranes, there being at least five chambers exclusive of the electrode chambers; passing a first source compound in ionic solution form through every second of the even numbered flow chambers; passing a second source compound in ionic solution form through the intermediate even numbered flow chambers, said second source compound being chemically dissimilar from said first source compound; passing through every second of the odd numbered chambers a liquid capable of maintaining the first product compound in solvated and electrically conductive form; passing through the intermediate odd numbered flow chambers a liquid capable of maintaining the second product compound in solvated and electrically conductive form; passing a direct electric current substantially transversely through said membranes and liquid flows flowing through said chambers, the direction of the current being such as to transfer anionic constituents through anion permeable membranes into the product chambers from one side and cationic constituents into the same chambers through cation permeable membranes from the other side, whereby also the exit of anionic constituents from the product chambers at the other side and the exit of the cationic constituents from the product chambers at the one side is barred by the anion passage resistance and the cation passage resistance of the respective membranes.

3. The process of forming two chemically dissimilar ionic product compounds in electrically conductive and solvated form by selective transfer into other fluid volumes of ionic constituents of two dissimilar source compounds in solution, the method comprising, disposing between an anode chamber and a cathode chamber at least five volumes of electrolytic liquids exclusive of the anolyte and the catholyte, the second volume and the fourth volume being liquids capable of maintaining a first and second product compound to be formed therein in solvated electrically conductive form, the first and the fifth volume being one of said source compounds in dissociated solvated form, and the third volume being 7 the other source compound in dissociated solvated form,

the other compound being chemically dissimilar from said one source compound, said one source compound comprising an ionic constituent of one polarity of the said first product compound and an ionic constituent of opposite polarity of the second product compound, said other source compound comprising an ionic constituent of said opposite polarity of said first product compound and an ionic constituent of said one polarity of said second product compound; establishing controlled ionic communication between said volumes by permselective barriers, the barrier between the said first and second volumes and the barrier between said third and fourth volumes being permeable to ions of said one polarity and passage resistant to ions of said opposite polarity, the barrier between said second and third volumes and the barrier between said fourth and fifth volumes being permeable to ions of said opposite polarity and passage resistant to ions of said one polarity; maintaining the volumes in a state of flow along the barrier surfaces; passing an electric direct current in series through said volumes and barriers, the direction of the current being such as to cause ions of said one polarity to migrate from said first volume into said second volume, whereby selected ionic constituents of the source compounds are electrically driven into said second and said fourth volume to form therein product compounds chemically distinct from said source compounds and distinct from each other.

July 1950, pp. 1390-1510, paper by Sollner. 

1. THE PROCESS OF FORMING TWO CHEMICALLY DISSIMILAR IONIC PRODUCT COMPOUNDS IN SOLVATED ELECTRICALLY CONDUCTIVE FORM BY SELECTIVE TRANSFER INTO OTHER FLUID VOLUMES OF IONIC CONSTITUENTS OF TWO CHEMICALLY DISSIMILAR SOURCE COMPOUNDS IN IONIC SOLUTION FORM, THE METHOD COMPRISING, DISPOSING BETWEEN AN ANODE CHAMBER AND A CATHODE CHAMBERE A PLURALITY OF VOLUMES OF ELECTRODIALYTIC LIQUID IN THIS ORDER: A FIRST SOURCE COMPOUND IN IONIC SOLUTION FORM, A LIQUID CAPABLE OF MAINTAINING A FIRST PRODUCT COMPOUND TO BE FORMED IN SOLVATED AND ELECTRICALLY CONDUCTIVE FORM, A SECOND SOURCE COMPOUND IN IONIC SOLUTION FORM, A LIQUID CAPABLE OF MAINTAINING A SECOND PRODUCT COMPOUND TO BE FORMED IN SOLVATED AND ELECTRICALLY CONDUCTIVE FORM, AND A FURTHER VOLUME OF SAID FIRST SOURCE COMPOUND IN IONIC SOLUTION FORM, SAID FIRST SOURCE COMPOUND BEING SO SELECTED AS TO COMPRISE AN IONIC CONSTITUENT OF ONE POLARITY OF SAID FIRST PRODUCT COMPOUND TO BE FORMED AND AN IONIC CONSTITUENT OF THE OPPOSITE POLARITY OF SAID SECOND PRODUCT COMPOUND TO BE FORMED, SAID SECOND SOURCE COMPOUND BEING SO SELECTED AS TO COMPRISES AN IONIC CONSTITUENT OF SAID OPPOSITE POLARITY OF SAID FIRST PRODUCT COMPOUND TO BE FORMED AND AN IONIC CONSTITUENT OF SAID ONE POLARITY OF SAID SECOND PRODUCT COMPOUND TO BE FORMED; ESTABLISHING CONTROLLED IONIC COMMUNICATION BETWEEN SAID VOLUMES BY PERMSELECTIVE BARRIES ARRANGED IN ALTERNATING ORDER, EACH SECOND BARRIER BEING PERMEABLE TO IONS OF ONE POLARITY AND PASSAGE RESISTANT TO IONS OF THE OPPOSITE PORALITY, THE REMAINING BARRIERS BEING PERMEABLE TO IONS OF SAID OPPOSITE POLARITY; APPLYING AN ELECTRICAL DIRECT POTENTIAL TO SAID ANODE AND SAID CATHODE TO DRIVE THE IONIC CONSTITUENTS OF SAID TWO SOURCE COMPOUNDS THROUGH SAID BARRIERS INTO SAID SOLUTION VOLUMES TO FORM TWO DISTINCT PRODUCT COMPOUNDS, THE FIRST PRODUCT COMPOUND COMPRISING A CONSTITUENT OF ONE POLARITY OF ONE SOURCE COMPOUND AND A CONSTITUENT OF THE OPPOSITE POLARITY OF THE OTHER SOURCE COMPOUND, THE OTHER PRODUCT COMPOUND COMPRISING A CONSTITUENT OF SAID OPPOSITE POLARITY OF SAID ONE SOURCE COMPOUND AND A CONSTITUENT OF SAID ONE POLARITY OF SAID OTHER SOURCE COMPOUND. 